Gibbs Free Energy

Introduction
In thermodynamics, the Gibbs free energy (IUPAC recommended name: Gibbs
energy or Gibbs function; also known as free enthalpy to distinguish it from
Helmholtz free energy) is a thermodynamic potential that measures the "useful" or
process-initiating work obtainable from a thermodynamic system at a constant
temperature and pressure (isothermal, isobaric). Just as in mechanics, where potential
energy is defined as capacity to do work, similarly different potentials have different
meanings. Gibbs energy is the capacity of a system to do non-mechanical work and ΔG
measures the non-mechanical work done on it. The Gibbs free energy is the maximum
amount of non-expansion work that can be extracted from a closed system; this
maximum can be attained only in a completely reversible process. When a system
changes from a well-defined initial state to a well-defined final state, the Gibbs free
energy ΔG equals the work exchanged by the system with its surroundings, minus the
work of the pressure forces, during a reversible transformation of the system from the
same initial state to the same final state.
Gibbs energy (also referred to as ∆G) is also the chemical potential that is minimized
when a system reaches equilibrium at constant pressure and temperature. Its derivative
with respect to the reaction coordinate of the system vanishes at the equilibrium point.
As such, it is a convenient criterion of spontaneity for processes with constant pressure
and temperature.
The Gibbs free energy, originally called available energy, was developed in the 1870s
by the American mathematician Josiah Willard Gibbs. In 1873, Gibbs described this
“available energy” as
the greatest amount of mechanical work which can be obtained from a given quantity of
a certain substance in a given initial state, without increasing its total volume or
allowing heat to pass to or from external bodies, except such as at the close of the
processes are left in their initial condition.
The initial state of the body, according to Gibbs, is supposed to be such that "the body
can be made to pass from it to states of dissipated energy by reversible processes." In
his 1876 magnum opus On the Equilibrium of Heterogeneous Substances, a graphical
analysis of multi-phase chemical systems, he engaged his thoughts on chemical free
energy in full.

History
In 1873, Willard Gibbs published A Method of Geometrical Representation of the
Thermodynamic Properties of Substances by Means of Surfaces, in which he
introduced the preliminary outline of the principles of his new equation able to predict or
estimate the tendencies of various natural processes to ensue when bodies or systems
are brought into contact. By studying the interactions of homogeneous substances in
contact, i.e., bodies, being in composition part solid, part liquid, and part vapor, and by
using a three-dimensional volume-entropy-internal energy graph, Gibbs was able to
determine three states of equilibrium, i.e., "necessarily stable", "neutral", and
"unstable", and whether or not changes would ensue.
Hence, in 1882, the German scientist Hermann von Helmholtz stated that affinity is the
largest quantity of work which can be gained when the reaction is carried out in a
reversible manner, e.g., electrical work in a reversible cell. The maximum work is thus
regarded as the diminution of the free, or available, energy of the system (Gibbs free
energy G at T = constant, P = constant or Helmholtz free energy F at T = constant, V =
constant), whilst the heat given out is usually a measure of the diminution of the total
energy of the system (Internal energy). Thus, G or F is the amount of energy “free” for
work under the given conditions.
Up until this point, the general view had been such that: “all chemical reactions drive
the system to a state of equilibrium in which the affinities of the reactions vanish”. Over
the next 60 years, the term affinity came to be replaced with the term free energy.
According to chemistry historian Henry Leicester, the influential 1923 textbook
Thermodynamics and the Free Energy of Chemical Reactions by Gilbert N. Lewis
and Merle Randall led to the replacement of the term “affinity” by the term “free
energy” in much of the English-speaking world.

Predicting Spontaneity
An increase in entropy;
• Changing from a more structured to less structured physical state:
• Solid to liquid
• Liquid to gas
• Increase in temperature causing a breakdown of structure within the states
• Fewer molecules becoming more molecules

Exothermic;
A lower energy state releasing energy is favorable
Gibbs Free Energy Equation
𝜟𝑮 = 𝜟𝑯 – 𝑻𝜟𝑺

If ΔG is negative (< 0) the reaction is favorable or spontaneous.

ΔH→ ΔS↓ Exothermic Endothermic
(-) (+)

Increasing Always Spontaneous Only spontaneous at

Entropy at any temperature high temperatures
(+)

Decreasing Only spontaneous at Never Spontaneous

Entropy low temperatures (but reverse is)
(-)

If ΔG is positive (> 0) the reaction is unfavorable or nonspontaneous

ΔH: is the enthalpy change of the system

T :is the temperature at which the reaction is occurring (in kelvin)
ΔS: is the entropy change of the system
Predicting Spontaneity based on the equation

𝜟𝑮 = 𝜟𝑯 − 𝑻𝜟𝑺
Distinction Between Spontaneity and Equilibrium

A + B AB

Equilibrium shifts gives the percentage of products and reactants under certain conditions.
But, implies that it is still spontaneous and some of each side are present. If ΔG is > 0
(positive), then there is no equilibrium and NO products are present. Reversible Reactions,
Entropy, and Le Chatelier’s Principle
 2NO2 (g) N2O4 (g)

NO2 is a brown gas, while N2O4 is a clear gas 𝜟𝑮 = 𝜟𝑯 – 𝑻𝜟𝑺

Gibbs Energy Analysis of Phase Equilibria

Equations of state are used to predict or to match equilibrium fluid phase behavior for systems
as diverse as distillation columns and miscible gas floods of oil reservoirs. The success of such
simulations depends on correct predictions of the number and the compositions of phases
present at a given temperature, pressure, and overall fluid composition. For example, recent
research has shown that three or more phases may exist in equilibrium in CO2 floods.
Advances in reservoir oil recovery methods have necessitated advances in methods for
prediction of phase equilibria associated with those methods. It was long considered sufficient
to approximate the reservoir behavior of oil and gas systems with models in which
compositions of the phases in equilibrium were unimportant.
In such a model, the amounts and properties of the phases are dependent on pressure and
temperature only.
Later, experience in production from condensate and volatile oil reservoirs showed that models
incorporating compositional effects were required to simulate the phase equilibria adequately.
This led to the use of con-vergence pressure correlations and subsequently to the development
of more sophisticated equation of state methods for modeling and predicting phase equilibria.
For adequate description of the compositional effects that occur in enhanced oil recovery
processes such as CO 2 and rich gas flooding, an equation-of-state approach is a virtual
necessity.
The use of equations of state for phase equilibrium prediction is not limited to the petroleum
industry. Such equations also find wide use in basic chemical and physical research, and in the
refining and chemical processing industries.
Solution techniques for phase equilibrium problems are varied and depend to some extent on
the application and equation of state used; however, there are three restrictions that all phase
equilibrium solutions must satisfy.
First, material balance must be preserved. Second, for phases in equilibrium there must be no
driving force to cause a net movement of any component from one phase to any other phase.
In thermodynamic parlance, the chemical potentials for each component must be the same in
all phases. Third, the system of predicted phases at the equilibrium state must have the lowest
possible Gibbs energy at the system temperature and pressure.
The requirement that the Gibbs energy of a system, at a given temperature and pressure, must
be a minimum is a statement of the second law of thermodynamics, equivalent to the more
common version requiring the entropy of an isolated system to be a maximum.
If the Gibbs energy of a predicted equilibrium state is greater than that of another state that
also satisfies Requirements I and 2, the state with the greater Gibbs energy is not
thermodynamically stable. Requirements I and 2, material balance and equality of chemical
potentials, are used commonly as the sole criteria for solution of phase equilibrium problems.
In many cases, there is no problem with this usage; however, there are important instances
when the Gibbs energy minimization requirement also must be considered. As discussed later,
equality of chemical potentials is necessary but not sufficient for minimization of the Gibbs
energy.
The iterative solution techniques usually used in finding equilibrium states may lead to a trivial
situation (all phases present having the same properties) that always will satisfy the first two
requirements but not necessarily the third. Of more importance perhaps, particularly in
enhanced oil recovery, is the possibility of predicting false two-phase states in or near a three-
phase region.
These states can satisfy material balance and chemical potential restrictions while failing to
minimize the Gibbs energy. This leads to predictions of incorrect phase volumes and properties
(density, viscosity, etc.), which can adversely affect the results of an oil recovery simulation.
Several authors have reported the occurrence of multiple (three or more) phases in rich gas/oil
and CO2 /oil reservoir systems. Others S- IO have shown that when there are multiple phases,
it is possible to predict equilibria at states that do not minimize the Gibbs energy of a system.
This paper describes such failures in solving the phase equilibria problem in terms of Gibbs
energy analysis. It also presents a method, and a mathematical proof supportive of the method,
for identifying false solutions.
For an elegant treatment of some properties of a Gibbs energy surface, Coleman, II Dunn and
Fosdick, Equations of state often are used to predict phase equilibrium solutions. Gibbs energy
analysis is the use of an equation of state to calculate a Gibbs energy surface and to determine
whether a predicted equilibrium state has the lowest possible Gibbs energy. We first illustrate
the use of a Gibbs energy surface to determine phase equilibria and show how false solutions
can be obtained. Then we describe a method for detecting false solutions and illustrate why it
succeeds when other methods fail.
Finally, we give specific examples of the utility of the method, using a version of the Redlich-
Kwong equation of state.
References
1. Matthew Schwartz Statistical Mechanics, Spring 2019 Lec8.
2. SPE 166448 Gibbs Free Energy Minimization for Reactive Flow in Porous Media
Ashwin Venkatraman, SPE, Larry W. Lake, SPE, The University of Texas at Austin
and Russell T. Johns, SPE, Pennsylvania State University
3. OCN 623 – Chemical Oceanography